Method of synthesising crystalline microporous metalloaluminophosphate for a solid body

ABSTRACT

The invention concerns a simple and cheap method for production of microporous crystalline metalloaluminiumphosphates (ELAPO) for use as adsorbent or catalyst by wholly or partially filling the pores of particles containing aluminium phosphate (AIPO) with an aqueous mixture containing an active source of metal and an organic structure directing agent and perform crystallisation at elevated temperature under autogenous pressure to form crystals of ELAPO.

The present invention concerns a method of synthesising metalloaluminophosphates (ELAPO), and more particularly to synthesisecrystalline microporous silico aluminophosphates (SAPO) of the molecularsieve type, from a solid body and also use of this product as a catalystfor methanol to olefin (MTO) production.

ELAPOs are molecular sieves which have a three-dimensional microporousframework structure of AlO₂, PO₂ and ELO₂ tetrahedral units. Generallythe ELAPOs have a chemical composition on an anhydrous basis expressedby the empirical formula of:(H_(w)El_(x)Al_(y)P_(z))O₂where EL is a metal selected from the group consisting of silicon,magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixturesthereof, “x” is the mole fraction of EL and has a value of at least0.005, “y” is the mole fraction of Al and has a value of at least 0.01,“z” is the mole fraction of P and has a value of at least 0.01, w is themole fraction of H and x+y+z=1.

The silico aluminium phosphates constitute a generic class ofnon-zeolite molecular sieve materials being capable of undergoingcomplete and reversible dehydration while retaining the same essentialframework topology in both the anhydrous and hydrated state.

The silico aluminium phosphates, SAPO-34 and SAPO-18, are the catalystsof choice for the MTO-reaction. SAPO-34 has chabasite (CHA) structureand is usually synthesised from an alumina source, a silica source, aphosporous source and at least one structure directing agent. Thisstructure directing agent is usually tetraethyl ammonium hydroxide(TEAOH). A water dispersion of the gel resulting from mixing thecomponents above, is hydrothermally treated at a temperature from150-260° C. under autogenous pressure to crystallise the SAPO-34. Thestructure directing agent is usually removed by heating in anoxygen-containing atmosphere (500-700° C.). The calcined materialcontains acidic protons and has catalytic properties.

In a traditional wet synthesis of SAPO-34 (as in U.S. Pat. No.4,440,871), the material crystallises with Si/Al ratio of 0.17,corresponding to what can be called high-Si SAPO-34. By altering thesynthesis conditions (Si/Al ratio lower than 0.17) it is possible toproduce a SAPO-34 with lower Si contents (U.S. Pat. No. 5,191,141 andU.S. Pat. No. 5,912,393). By using Si/Al ratios lower than 0.17 one canalso obtain structures with AEI structure (SAPO-18; U.S. Pat. No.5,609,843), intergrowths of SAPO-34 and SAPO-18 (U.S. Pat. No.6,334,994) or AFI-structure (SAPO-5). In a typical wet synthesis ofSAPO-18, the structure crystallises with a Si/Al ratio of 0.06. XRDanalysis will reveal information on the presence of SAPO-34 or SAPO-18.These structures are defined in Atlas of Zeolites Structure Types, W. M.Meier and D. H. Olson, Second Revised Edition 1987, by Butterworths.

U.S. Pat. No. 4,861,743 teaches a process for the production of acrystalline non-zeolitic molecular sieve in a pre-formed body orcarrier. Contacting a liquid reaction mixture with spray-dried particlesor extrudates of alumina or silica-alumina at hydrothermal conditionsproduces the crystalline non-zeolitic molecular sieve. The liquidreaction mixture contains a reactive source of phosphorous pentoxide andan organic structure directing agent. The crystallisation takes place atelevated pressure and temperature and the preformed body reacts with theliquid mixture to form non-zeolitic molecular sieves within the body.Phosphorous can be an active component in the liquid or on the solidalumina or silica-alumina. Likewise, if the non-zeolitic molecular sievecontains silica, the reactive source of silica can be included in thebody and/or in the liquid reaction mixture. If the non-zeoliticmolecular sieve is to contain one or more elements other than aluminium,silicon and phosphorus, the reactive sources of these elements may beincluded in the silica or silica-alumina body and/or in the liquidreaction mixture. The smallest amount of water used in this procedure is25 moles of water per mole of aluminium. Thus, only alumina orsilica-alumina is used as the preformed body. All other reactivecomponents are either impregnated on the body or in the liquid mixture.The preparation method that is described is liquid synthesis with excessliquid that needs to be removed afterwards.

In U.S. Pat. No. 5,514,362 synthesis of SAPO-5, SAPO-11, SAPO-31 andSAPO-39 from dense mixtures of alumina and silica gel is described, withno excess liquid to be removed. The dense gel can be formed intoself-supporting particles and the shape of the particles is preservedafter crystallisation. The gel comprises alumina, silica, structuredirecting agent and an active source of phosphorous. In all examples thedense gel is extruded into particles before the crystallisation processtakes place. The molecular sieve crystallites formed are smaller thanthose generally formed in conventional processes.

European Patent Application No. 1002764 describes a method for thepreparation of small zeolite crystals inside a porous support materialwith pores smaller than 1000 Å. In this way the size of the zeolitecrystals can be controlled. The porous support material is preferablyremovable in order to isolate the pure zeolite or it is useful ascomponent of a desired catalyst. Typical support materials are carbon ormagnesium oxide representing the group of removable porous supportmaterials and silica alumina, which may be a desirable constituent ofthe catalyst. To obtain the product the support material is impregnatedwith a synthesis gel consisting essentially of a zeolite precursorcomposition comprising hydrated oxides of Si, Al and P, metal compoundsand a zeolite structure directing agent. The advantages of the methodare to prepare small crystallites and the porous support material isused to control the crystallite size. The porous support material is notan active source of the crystallised zeolite.

U.S. Pat. No. 6,004,527 relates to a “dry” process for the production ofa large pore molecular sieve by impregnating a solid cationoxide-framework-structure with other reagents suitable for hydrothermalreaction between these reagents and the solid cationoxide-framework-structure to form an impregnated paste-free composition.Then the impregnated paste-free composition is subjected to conditionsof temperature and pressure to effect a hydrothermal reaction andconvert the reagents of the reaction into a crystalline molecular sievethat possesses the morphologic characteristics of the solid cationoxide-framework-structure. Production of zeolite particles from silicais exemplified.

One object of the present invention is to obtain a cheap, simple andenvironmentally friendly production method for catalysts and adsorbantsof the metallo alumino phosphate type (ELAPO). Production ofsilicoaluminophosphate (SAPO) is of special interest.

Another object is to synthesise SAPO crystallites with suitable size andcomposition for methanol to olefin production. It is of special interestto produce materials containing SAPO-34, SAPO-17 and/or SAPO-18, thesematerials being suitable for the methanol to olefins (MTO) reaction. Athird object is, through the synthesis of SAPO-5, SAPO-11 and SAPO-20 toshow the general applicability of the described synthesis method.

These and other objects of the invention are obtained with the method asdescribed below. The invention is further defined and characterised bythe enclosed patent claims. The invention will be further documentedwith reference to the FIGS. 1-14, where:

FIG. 1 shows the XRD pattern of the product from Example 1.

FIG. 2 shows XRD patterns of the products from Examples 2 and 3.

FIG. 3 shows XRD patterns of the products from Examples 4-8.

FIG. 4 shows the XRD pattern of the product from Example 9.

FIG. 5A shows XRD patterns of the products from Examples 10-14.

FIG. 5B shows XRD patterns of the products from Examples 15-19.

FIG. 6 shows XRD patterns of the products from Examples 20-22.

FIG. 7A shows the XRD pattern of the product from Example 23.

FIG. 7B shows SAPO-34 crystallites.

FIG. 8 shows the XRD patterns of the products from Examples 24-25.

FIG. 9 shows the XRD patterns of the products from Examples 26-29.

FIG. 10 shows the XRD pattern of the products from Example 30.

FIG. 11 shows the XRD patterns of the products from Examples 31-32.

FIG. 12 shows the XRD pattern of the product from Example 33.

FIG. 13 shows the XRD patterns of the product from Examples 34-36.

FIG. 14 shows the XRD patterns of the product from Examples 37-38

The invention thus concerns a method of synthesising crystallinemicroporous metallo alumino phosphate (ELAPO) from a solid body, wherethe body consists of particles containing Al and P. The pores of theparticles are wholly or partly filled with a liquid reaction mixture,comprising an active source of the EL metal, an organic structuredirecting agent and water. The crystallisation is performed at elevatedtemperature under autogenous pressure to form crystals of microporousELAPO, where the EL metal is selected from the group consisting ofsilicon, magnesium, zinc, iron, cobolt, nickel, manganese, chromium andmixtures thereof. The EL metal could also be part of the solid body andin this case the liquid reaction mixture could be used with or withoutan active source of the EL metal. It is preferred to use silicon as theEL metal and produce crystalline microporous SAPO. AlPO particles couldbe contained in the body and they could also have an outer silica shell.It is preferred to use AlPO where P/Al=1.2-0.6 and to carry out thesynthesis in the absence of an external liquid. The particles could becalcined prior to the treatment. The hydrothermal reaction time is 2-120hours, preferably 4-20 hours. The crystallisation should be performed attemperatures from 150-260° C., preferably 200-220° C. The structuredirecting agent may be selected from tetraethyl ammonium hydroxide(TEAOH), isopropylamine (IPA), di-isopropylamine (DPA), tripropylamine(TPA), cyclohexylamine (CHA), tri-ethylamine (TEA) ortetramethyl-ammonium-hydroxide (TMAOH). The ratio between the liquidvolume and pore volume (measured by liquid volumetric N₂ adsorption) is0.1-7, preferably 1-4 and most preferably 1-3. Surprisingly it was alsofound that it was possible to produce SAPO from a reaction mixturewithout stirring of the reactants. It is preferred to produce SAPO-34,SAPO-17 and/or SAPO-18. SAPO-5, SAPO-11 and SAPO-20 could also beproduced. The product could be used as adsorbant or as catalyst for theconversion of methanol to light olefins. The particles produced couldalso be used as catalysts for the production of olefins from anoxygenate containing feedstock comprising at least one compound selectedfrom the group consisting of methanol, ethanol, n-propanol,iso-propanol, C4-C20 alcohols, methyl ethyl ether, dimethyl ether,diethyl ether, di-isopropyl ether, formaldehyde, dimethyl carbonate,dimethyl ketone, acetic acid and mixtures thereof.

With the expression “pores” is meant all pores in the product, while“pore volume” is the volume as measured by liquid volumetric N₂adsorption.

In contrast to earlier known preparation methods, aluminium phosphatecould be used as the active source for both aluminium and phosphorouswhen preparing ELAPOs. The aluminium phosphate is used in the form ofporous particles. The AlPO particles might be precipitated by variousmethods, depending on the desired properties.

For preparation of SAPOs, silica sol or fumed silica are preferredactive sources of silicon. Silica gel and silica hydrogel, silicates,silicic acid, colloidal silica, silica hydroxides, alkoxides of silicon,and reactive solid amorphous precipitated silica are also suitable. Thesilica may be prereacted with the solution of the structure directingagent, or silica may be present as a physical mixture with the porousaluminiumphospate, or as a silico aluminium phosphate.

An organic structure directing agent is added to facilitatecrystallisation of the molecular sieve. A mixture of two or moredifferent structure directing agents could also be used. Suitablestructure directing agents include tetraethyl ammonium hydroxide(TEAOH), isopropylamine (IPA), di-isopropylamine (DPA), tripropylamine(TPA), cyclohexylamine (CHA), tri-ethylamine (FEA) andtetramethyl-ammonium-hydroxide (TMAOH).

For the preparation of SAPOs, porous AlPO particles are mixed with asmall amount of water, a silicon source and a solution containing astructure directing agent to saturate the pores of the particles. Thewater content is so small that the mixture appears dry, thus the term“dry synthesis” is used. Another term for this technique is incipientwetness. Alternatively the Si source can be present as a separate phaseof the solid AlPO or as a silico aluminium phosphate mixture. Slightlydifferent mixing procedures may be used in preparing the reactionmixtures, for instance, by changing the order of which the fluids andAlPO are added. Preferably, the mixing of reactants is performed by anincipient wetness technique and will result in a liquid volume-to-porevolume ratio between approximately 0.1-7, preferably 1-4, and mostpreferably 1-3. The reaction mixture is placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluorethylene. The reaction mixture is heated under autogenouspressure at a temperature in the range of 150° C. to 260° C., preferablyat a temperature of 200-220° C. for a period of from a few hours to somedays, typically 2-120 hours, preferably about 4-20 hours. Thecrystallisation occurs in absence of a continuous liquid phase. The ideais that one or more SAPOs (e.g. SAPO-34/SAPO-18/SAPO-5) are nucleatedinside the pores of the carrier particle. The as synthesised product iscalcined at 500-600° C. for a few hours in dry air in order to removethe organic structure directing agent from the pores of the crystallinematerial. The resulting molecular sieve comprises a three-dimensionalmicroporous crystal framework comprising a SAPO microporous structure.

After SAPO synthesis, particles may be prepared from a mixture of thecrystallised material and a suitable binder (e.g. fluidised bedparticles).

Materials suitable for use in fluidised bed reactors are typicallyproduced by spray-drying a slurry of the active catalyst. Additionalmaterials are generally added to the slurry in order to adjust thephysical properties and the mechanical strength of the final particle.

When preparing SAPO-34 by “dry-synthesis” from a porous AlPO mixed witha silica source and structure directing agent /water solution thefollowing substitution will take place:1/n Si(OH)₄(sol)+AlPO₄(s)→(HSi)_(1/n)AlP_(1-1n)O₄(s)+1/nH₃PO₄(l)where n>1.

This corresponds to using 1 mol base/Si and up to 3 moles of base toneutralise the phosphoric acid. Since it is probably not necessary witha complete neutralisation (3 moles of base) of the phosphoric acid, only1-2 moles of base may be adequate for this neutralisation.

This suggests that an AlPO having P/Al of approximately 0.8 (1.2-0.6) ismore suitable for synthesis of SAPO-34 with Si/Al ratio 0.17. Forsynthesis of SAPO-34/SAPO-18 with Si/Al ratio around 0.06 it is moresuitable with an AlPO with P/Al of 0.9-1. One advantage of using an AlPOwith P/Al ratio adjusted to the amount of Si used in the synthesis, isto minimise the amount of structure directing agent needed for thesynthesis, or for making extra base addition unnecessary.

It would also (when using AlPO with P/Al=1) be unnecessary to use themore costly template, TEAOH, as a neutralising agent. For instance,isopropyl amine (IPA) may be used. Hence, to make the synthesis morecost-effective a significant amount of the structure directing agentTEAOH may be replaced by IPA.

The present synthesis method has the following advantages compared toprior art:

-   -   A. The use of a porous AlPO as precursor for the microporous        crystalline silico-aluminophosphate makes it possible to use        considerably smaller amounts of structure directing agent, as        well as making it possible to use cheaper amines as part of a        structure directing agent mixture.    -   B. The use of less water (compared to H₂O/Al=25 in U.S. Pat. No.        4,861,743 and H₂O/Al=17.5-22.5 in U.S. Pat. No. 6,207,872 and        H₂O/Al=15 in Lok et al U.S. Pat. No. 4,440,871 (Example 25),        H₂O/Al are mainly 5-10 in this invention) during the        hydrothermal synthesis compared to prior art, makes it        unnecessary to filtrate and wash the product and avoids cleanup        of contaminated water.    -   C. The intimate mixing of liquid and solid established in        filling the pores of the solid with the synthesis liquid makes        stirring of the synthesis mixture unnecessary, simpler        autoclaves could thus be used for the hydrothermal synthesis        stage.    -   D. The intimate contact between solid and liquid also gives a        higher nucleation rate and a higher crystallisation rate,        resulting in less reaction times needed, and giving crystallites        of size 0.2-1 μm, compared to 0.5-3 μm for a SAPO-34 synthesised        after the method of Lok et.al in U.S. Pat. No. 4,440,871. The        smaller particle size gives a MTO catalyst with higher        durability and expected higher rate of absorption.    -   E. By using this method it is possible to vary the Si/Al ratio        to a wide extent and obtaining SAPO-34 as well as SAPO-18. By        using Si/Al ratios in the range of 0.03-0.06, materials        containing SAPO-34, SAPO-18 and mixtures thereof in various        proportions can be made. Under certain process conditions, these        may have improved deactivation properties as well as higher        olefin selectivities in the MTO process.

EXAMPLES

The invention will be further illustrated by the examples to follow.

A description with characteristics of the different AlPO materials usedin the present invention is given in Table 1. The porosity of thematerials was characterised by liquid N₂ adsorption and elementalcomposition by XRF. TABLE 1 Characteristics of the different AlPOs usedin the present invention. Unless otherwise stated in the text, allsamples were calcined at 400° C. for 16 hours before use. N₂- N₂- PoreBET volume diameter Name Preparation P/Al (m²/g) (cc/g) (Å) AlPO-lightCommercial, 1.1 14 Riedel-de-Hahn; EG-no.: 232-056-9; Lot 914110calcined 600° C. K00-053.001 Powder from 1.0¹⁾ 100 0.66 220 Grace,Worms, Germany, LOT SP2 7980-01 K00-058.001 Powder produced²⁾, 0.8 2300.41 60 aceton washed, vacuum dried, calcined K00-077.001 Powder from1.0¹⁾ 106 0.71 220 Grace, Worms, Germany, LOT SP2 7980-02 K00-077.008K00-077.001 spray 0.9 140 0.64 180 dried K00-102.003 Powder produced²⁾,0.95 177 0.47 90 spray dried K00-092.004 Powder produced²⁾, 1.0 160 0.44100 spray dried K00-218.002 Powder produced²⁾ 1.0 192 0.60 100¹⁾specification from supplier²⁾synthesised according to the method given in U.S. Pat. No. 4364855

Preparation of the Aluminium Phosphates Used

The aluminium phosphate powders produced and given in Table 1 weresynthesised according to the method given in U.S. Pat. No. 4,364,855.The resulting gels were washed and filtrated repeatedly to removeNH₄NO₃, followed by drying at 100° C. and calcination in an oven at 400°C. for 16 h. The spray dried samples were produced from a water slurryin a conventional spray drier. The material denoted K00-092.004 wasspray dried from a slurry with added Ludox LS30 so as to have 20 weight% SiO₂ in the final particle.

If not otherwise stated in the text, a stainless steel autoclave with aTeflon liner of volume 40 ml was used and a synthesis temperature of210° C. A detailed overview of all synthesis presented in this inventionare listed in Table 2.

If not otherwise stated, the following reagents are used:

-   -   Silica source: Ludox LS30; 30 weight % suspension in water        (pH=8.2), Du Pont product    -   TEAOH (tetraethyl ammonium hydroxide; Aldrich; 35 weight %)    -   IPA (isopropylamine; Fluka; 99.5 weight %)    -   DPA (di-isopropylamine; Fluka; 99 Weight %)    -   TEA (Tri-ethylamine, Janssen 99% 15.791.77)    -   TPA (Tripropylamine, Fluka, 98 weight %)    -   TMAOH (Tetramethyl ammonium hydroxide-pentahydrate; Fluka, 9        weight %)

The AlPO materials used in this invention are detailed in Table 1.

XRD Analysis

The products were analysed using an X-ray powder diffractometer, SiemensD-5000, which produces monochromatic radiation (from a CuK_(α1) source)of wavelength equal to 1.54056 Å. Most of the XRD patterns presented inthis invention are displayed along with the XRD pattern of a referenceSAPO-34 obtained by a conventional wet synthesis procedure essentiallylike that in U.S. Pat. No. 4,440,871 (B. M. Lok et al., Example 35). Thediffraction pattern of this latter reference sample is denoted “RUW” inthe Figures. TABLE 2 A detailed overview of all synthesis presented inthe present invention Ex Mass weights (g) Mol-weight (mmol) Time¹⁾ no.AlPO Sample AlPO Ludox TEAOH IPA Water AlPO SiO2 TEAOH IPA Water V/V_(p)(hours)  1 AlPO-light EWH8-16 8.0 2.0 14.0 0 5.0 66 10 33 0  861 72  2AlPO-light EWH8-10 5.0 3.1 8.8 0 3.1 41 16 21 0  362²⁾ 42  3 AlPO-lightEWH8-11 5.0 3.1 8.8 0 3.1 41 16 21 0  125³⁾ 42  4 K00-053.001 EWH11-62.0 0.26 1.86 0 0 16.4 1.3 4.4 0  77.3 ˜2.5 20  5 K00-058.001 EWH12-42.0 0.85 1.78 0 0 16.4 4.2 4.2 0  97 ˜2.0 20  6 K00-077.008 EWH15-8 2.01.18 2.48 0 0 16.4 5.9 5.9 0  135 ˜2.5 20  7 K00-102.003 EWH16-7 2.01.52 3.2 0 0 16.4 7.6 7.6 0  175 ˜4.7 20  8 K00-092.004 EWH17-8 2.0 0.122.6 0 0 16.4 0.62/7⁴⁾ 6.2 0  99 ˜3.0 20  9 K00-092.004 EWH17-4 2.0 0 2.70 0 16.4   0/7⁴⁾ 6.4 0  98 ˜3.0 20 10 K00-218.002 ABA135-1 2.0 0.55 2.30 0 16.4 2.7 5.5 0  104 20 11 K00-218.002 ABA135-2 2.0 0.55 2.3 0.16 016.4 2.7 5.5 2.7  104 20 12 K00-218.002 ABA135-3 2.0 0.55 2.3 0.32 016.4 2.7 5.5 5.4  104 20 13 K00-218.002 ABA135-4 2.0 0.55 2.3 0.48 016.4 2.7 5.5 8.1  104 20 14 K00-218.002 ABA135-5 2.0 0.55 2.3 0.64 016.4 2.7 5.5 10.8  104 20 15 K00-218.002 ABA136-1 2.0 0.55 0 0.32 1.8216.4 2.7 0 5.4  122 20 16 K00-218.002 ABA136-2 2.0 0.55 1.15 0.32 0.6816.4 2.7 2.7 5.4  100 20 17 K00-218.002 ABA136-3 2.0 0.55 2.3 0.32 016.4 2.7 5.5 5.4  104 20 18 K00-218.002 ABA136-4 2.0 0.55 3.45 0.32 016.4 2.7 8.2 5.4  145 20 19 K00-218.002 ABA136-5 2.0 0.55 4.60 0.32 016.4 2.7 10.9 5.4  187 20 20 K00-092.004 EWH18-1 2.0 0 6.1 0 0 16.4  0/7⁴⁾ 14.5 0  220 ˜6.8 20 21 K00-092.004 EWH18-2 2.0 0 3.8 0.34 1.5016.4   0/7⁴⁾ 9.0 5.8  220 ˜6.5 20 22 K00-092.004 EWH18-4 2.0 0 0 0.854.0 16.4   0/7⁴⁾ 0 14.4  222 ˜5.9 20 23 K00-218.002 ABA127 60 16.4 69.10 0 492 82 164 0 3133 20 24 K00-218.002 ABA139-3 2.0 0.55 2.3 0 0 16.42.7 5.5 0  104 20 25 K00-218.002 ABA139-4 2.0 0.55 2.3 0 0 16.4 2.7 5.50  104 20 26 K00-218.002 ABA140-1 2.0 0.55 2.3 0 0 16.4 2.7 5.5 0  10420 27 K00-218.002 ABA140-2 2.0 0.55 2.3 0 0.5 16.4 2.7 5.5 0  132 20 28K00-218.002 ABA140-3 2.0 0.55 2.3 0 1.0 16.4 2.7 5.5 0  160 20 29K00-218.002 ABA140-4 2.0 0.55 2.3 0 3.0 16.4 2.7 5.5 0  271 20 30K00-053.001 ABA143-4 2.0 0.55 0 0.78⁵⁾ 3.0 16.4 3.8 0 5.4  186 ˜5.4 2031 K00-053.001 ABA145-2 2.0 0.55 0 0.66⁶⁾ 3.2 16.4 2.7 0 3.6  218 ˜4.820 32 K00-053-001 ABA145-4 2.0 0.55 0 0.99⁶⁾ 2.6 16.4 2.7 0 5.4  193˜4.3 20 33 K00-058.001 ABA144-2 2.0 0.55 0 0.37⁷⁾ 3.2 16.4 2.7 0 3.7 199 ˜3.2 20 34 K00-218.002 ABA146-1 2.0 0.55 2.3 0 0 16.4 2.7 5.5 0 104 20 35 K00-218.002 ABA146-2 2.0 0.55 2.3 0 0 16.4 2.7 5.5 0  104  836 K00-218.002 ABA146-3 2.0 0.55 2.3 0 0 16.4 2.7 5.5 0  104  4 37K00-058.001 ABA147-2 2.0 0.8 0.8 0 1.4 16.4 3.8 1.9 0  136 20 38K00-058.001 ABA151-3 2.0 0.4 0.8 0 1.7 16.4 1.9 1.9 0  138 20 41⁸⁾K00-218.002 ABA-201-1 2.44 0.67 4.2 0 0 20 3.3 10 0  178 ˜3.3 77⁸⁾ 42⁸⁾K00-218.002 ABA-201-2 2.44 0.22 4.2 0 0 20 1.1 10 0  160 ˜3.0 77⁸⁾ 43K00-218.002 ABA-202-2 2.44 0.22 4.2 0 0 20 1.1 10 0  160 ˜3.0 20 44⁹⁾K00-218.002 ABA-204-2 2.44 0.22 4.2 0 0 20 1.1 10 0  160 ˜3.0 16 + 48⁹⁾45 K00-218.002 ABA 208-1 2.44 0.22 2.10 0 2 20 1.1 5 0  196 ˜3.0 20 46K00-218.002 ABA-207-2 2.44 0.22 2.86 0 0.8 20 1.1 6.8 0  156 ˜2.6 20 47K00-218.002 ABA-208-2 2.44 0.22 3.53 0 0.5 20 1.1 8.4 0  164 ˜2.9 20 48K00-218.002 ABA-207-1 2.44 0.22 4.2 0 0 20 1.1 10 0  160 ˜3.0 20 49K00-218.002 ABA-210-2 2.44 0.22 1.43 0.34¹⁰⁾ 1.9 20 1.1 3.4 ¹⁰⁾  166˜2.7 20 50 K00-218.002 ABA-208-6 2.44 0.44 2.86 0 1.0 20 2.2 6.8 0  176˜2.9 20 51 K00-218.002 ABA-208-5 2.44 0.11 2.86 0 1.2 20 0.6 6.8 0  174˜2.8 20¹⁾Hydrothermal reaction time, 210° C. if no otherwise stated²⁾Approximately 80 wt % of the water within the reaction mixture wasevaporated prior to hydrothermal treatment,³⁾Approximately 40 wt % of the water within the reaction mixture wasevaporated prior to hydrothermal treatment,⁴⁾x/y where x represents the amount ofSiO_(2 from Ludox and y represents the amount of SiO) ₂ within the outershell of the AlPO,⁵⁾Tripropylamine⁶⁾Tetramethylammoniumhydroxide,⁷⁾Diisopropylamine,⁸⁾The relative amounts of structure directing agent and Si as well ascrystallisation temperature were taken from: U.S. Pat. No. 5191141,Example 5, 77 h at 175° C.,⁹⁾The relative amounts of structure directing agent and Si as well ascrystallisation temperature were taken from: U.S. Pat. No. 5912393,Example 1, 16 h at 100° C., 48 h at 175° C.,¹⁰⁾Tri-ethylamine

Example 1 Synthesis of SAPO-34 from AlPO-particles (EWH8-16)

A synthesis mixture was prepared by first adding 2.0 g Ludox LS30 to 8.0g of a porous AlPO material (K00-102.003, Table 1) and then adding 14.0g 35% TEAOH and 5.0 g water under thorough mixing. 0.35 g of HCl wasadded to the water before mixing. The mixture was reacted in a Teflonlined stainless steel autoclave at 210° C. for 72 h. The XRD pattern ofthe resulting silicoaluminophosphate product is shown in FIG. 1(EWH8-16), and confirms the formation of an almost pure SAPO-34. Thereflection at about 2Θ=26 degrees is assumed to represent a dense AlPO₄phase.

Example 2 Fractional Removal of Water Prior to Hydrothermal Treatment(EWH8-10)

In this preparation, 5.0 g AlPO-light (Table 1) was used as an AlPOsource and mixed with 3.1 g Ludox LS30, 8.8 g TEAOH and 3.1 g waterusing the mixing procedure outlined in Example 2.

The mixture was heated in an oven at 97° C. until the liquid mass wasreduced from 15.0 g to 6.2 g, corresponding to a loss by evaporation of8.8 g of water, or approximately 80% of the total water content withinthe original mixture. The mixture was reacted in a Teflon linedstainless steel autoclave at 210° C. for 42 h, and the XRD pattern inFIG. 2 confirms that SAPO-34 was formed.

Example 3 Fractional Removal of Water Prior to Hydrothermal Treatment(EWH8-11)

This preparation is identical to the one in Example 2 except that theamount of water being evaporated was somewhat less, approximately 40weight % of the total water content within the original sample. The XRDpattern in FIG. 2 confirms that SAPO-34 was formed.

Examples 4-8 Synthesis of SAPO-34 from Different AlPOs (EWH1-6, 12-4,15-8, 16-7, 17-8)

Five different AlPOs denoted K00-053.001. K00-058.001, K00-077.008,K00-102.003 and K00-092.004 (see Table 1) were tested. In contrast tothe preceding synthesis (Examples 1-3), only 2.0 g of AlPO was used ineach of the present examples. Also, the “free” volume or the available“gas-volume” of the Teflon-liner was reduced from approximately 40 ml to3-5 ml by insertion of a compact, cylindrical Teflon insert into theTeflon-liner. The reason for reducing this “free” volume was to limitthe amount of water in the vapour phase.

Also, a slightly different mixing procedure was applied as compared tothe one described in Examples 2-3, in that Ludox LS30 (0.26 g, 0.85 g,1.18 g, 1.52 g, 0.12 g respectively), was mixed together with theorganic structure directing agent TEAOH (1.86 g, 1.78 g, 2.48 g, 3.2 g,2.6 g respectively), and the resulting solution added to the AlPO powderby incipient wetness by thorough mixing.

The mixtures were reacted in Teflon lined stainless steel autoclaves at210° C. for 20 h. The XRD patterns of the crystalline products (FIG. 3)are all consistent with the formation of SAPO-34. The numerous,additional intense diffraction lines seen in the XRD pattern of sampleEWH11-6 originate from aluminium ammoniumhydroxidephosphate.

Example 9 Synthesis of SAPO-34 in the Absence of Ludox (EWH17-4)

The surface of one of the AlPO materials (K00-092.004; Table 1)contained a silica shell, which was formed by spray-drying. The silicacontent was approximately 20 weight %. 2.7 g TEAOH was added to 2.0 g ofthe AlPO material by incipient wetness under thorough mixing. Themixture was reacted in a Teflon lined stainless steel autoclave at 210°C. for 20 h. The XRD pattern of the resulting crystalline powdersrevealed formation of pure SAPO-34 (FIG. 4).

Examples 10-19 Mixture of Two Organic Structure Directing Agents WithinOne Reaction Mixture (ABA135-1-51136-1-5)

In the following examples, two different synthesis approaches wereapplied; a) the Si-content and the TEAOH/Si-mole ratio were keptconstant and the IPA/Si-mole ratio varied and b) the Si-content and theIPA/Si-mole ratio were kept constant and the TEAOH/Si-mole ratio varied.Table 2 shows the actual amount of reactants used. The AlPO used inthese synthesis was K00-218.002 (Table 1). In these Examples Ludox, theorganic structure directing agent (s) and AlPO were mixed together andwater subsequently added by incipient wetness under thorough mixing.

As in Examples 4-8, the available “free” volume of the Teflon-liner wasreduced from approximately 40 ml to only 3-5 ml by inserting a compact,cylindrical Teflon insert into the Teflon-liner. The mixtures werereacted in Teflon lined stainless steel autoclaves at 210° C. for 20 h.

As indicated by the XRD patterns of the crystalline products (FIGS. 5Aand B), SAPO-34 are formed in all preparations, except for ABA-136-1, inwhich only isopropylamine (IPA) was used as an organic additive.

Two of the synthesised products, ABA-135-5 and ABA-136-2 seem to consistof mostly pure SAPO-34. Both of these samples had—prior to synthesis—thesame molar ratio of 2.0 between IPA and TEAOH. Sample ABA-135-5contained, however, twice as much structure directing agent as comparedto sample ABA-136-2.

The XRD patterns of most of the products reveal some minor formation ofSAPO-18, as suggested—tentatively—by the appearance of diffraction line2θ=17.0 degrees. As can be concluded from the data in FIG. 5 A, therelative amount of SAPO-34/SAPO-18 depends on the relative concentrationof reactants (Table 2) within the synthesis mixture.

Examples 20-22 Mixture of Structure Directing Agents in the Absence ofLudox (EWH18-1, 2 and 4)

Using essentially the same procedure as in Examples 10-19 and replacingthe AlPO with K00-092.004 (Table 1) three reaction mixtures wereprepared in the absence of Ludox. The composition of the reactionmixtures is summarised in Table 2. The mixtures were reacted in Teflonlined stainless steel autoclaves at 210° C. for 20 h.

The XRD pattern of the resulting crystalline powders revealed formationof SAPO-34 (FIG. 6). However, when increasing the relative amount of IPAwhile keeping the total amount of organic additives (TEAOH and IPA)constant (Table 2), some additional small amount of other crystallinespecie(s) were formed.

Example 23 Upscaling (ABA127)

An attempt to upscale the synthesis of SAPO-34 was initiated byincreasing the amount of all reactants by a factor of 30 in comparisonto Example 10. The smaller Teflon autoclave (40 ml) was replaced by alarger one of approximately 200 ml. Five identical batches wereprepared, using 60 g of the AlPO material denoted K00-218.002 in each(Table 1), 16.4 g Ludox LS30 and 69.1 g TEAOH. The reactants were mixedas described in Examples 4-8. The overall liquid volume wasapproximately twice the available pore volume of the porous AlPOmaterial.

The XRD pattern of the resulting crystalline powders revealedessentially SAPO-34 (FIG. 7A). Some small amount of AlPO-18/SAPO-18seems to form, as tentatively concluded from the observed diffractionline at 2θ=17.0 degrees. The XRD of only one of the replicas is shown inFIG. 7A, simply due to the excellent reproducibility observed for thefive batches.

The size of the regularly shaped SAPO crystallites are typically in therange 0.25 to 1 μm as seen in FIG. 7B.

Examples 24-25 Non-Stirring of Reactants Prior to HydrothermalTreatment. (ABA139-3 and 4)

2.0 g of an AlPO material K00-218.002 (see Table 1) was mixed with 0.55g Ludox LS30 together with 2.3 g of an organic additive (TEAOH). Waterwas subsequently added by incipient wetness under thorough mixing(ABA139-3). To a second and identical AlPO material was added the sametype and amount of fluid reactants, without any stirring (ABA139-4). SeeTable 2 for further details. Both mixtures were reacted in Teflon linedstainless steel autoclaves at 210° C. for 20 h.

As can be confirmed by the XRD patterns (FIG. 8), the two crystallineproducts were identical. Moreover, the intensities (areas) of thecorresponding diffraction lines of the two samples were identical,suggesting that stirring or non-stirring of reactants prior tohydrothermal treatment is of little relevance regarding the subsequentproduct distribution after hydrothermal treatment. The results indicatethat stirring is not a critical factor, so that no special precautionsneed to be taken in production, which is cost saving.

Examples 26-29 Effect of Water Within the Reaction Mixture (ABA140-1, 2,3 and 4)

Four AlPO powder samples, each 2.0 g, (K00-218.002; Table 1) were mixedwith 2.3 g 35% TEAOH, 0.55 g Ludox LS30 and water according to the samemixing procedure as outlined in Example 24. The difference between thereaction mixtures used in the present Examples and the correspondingreaction mixture in Example 25 was the proportion of water used (Table2). The water content was varied with 0, 0.5, 1.0 and 3.0 in therespective mixtures. The mixtures were reacted in Teflon lined stainlesssteel autoclaves at 210° C. for 20 h.

As was confirmed by the XRD patterns in FIG. 9, the resulting productswere identical. Moreover, the intensities (areas) of the differentdiffraction lines of the four samples were identical, suggesting theaddition of “external” water to have no significant effect on theproduct distribution. This result is probably not too surprising, sincemost of the reactants contain some “inherent” water, i.e., watercontained within the actual chemical reactants used in the presentsynthesis (for instance 35% TEAOH and Ludox LS-30).

Example 30 Preparation of SAPO-5 (ABA143-4)

2.0 g of an AlPO “K00-058.001” powder sample (Table 1) was mixed with0.78 g Tripropylamine, 0.55 g Ludox LS30 and 3.0 g water. The mixing andcrystallisation procedures were the same as described in Example 24.

The reference XRD pattern of SAPO-5 (FIG. 11; see “collection ofsimulated XRD powder patterns for zeolites”, third revised edition, M.M. J. Treacy, J. B. Higgins and R. von Ballmoos, 1996) proves that asignificant amount of SAPO-5 is formed from the above synthesisreaction. However, the SAPO-5 formed is not pure.

Examples 31-32 Preparation of SAPO-20 (ABA145-4, ABA-145-2)

The same type of AlPO powder as used in Example 31 (“K00-058.001”;Table 1) was mixed with Tetramethylammoniumhydroxide-pentahydrate, LudoxLS30 and water according to the same mixing and crystallisationprocedure as described in Example 24. Two synthesis reactions wereinitiated. The amount of reactants used is shown in Table 2.

The reference XRD pattern of SAPO-20 (FIG. 11; see “collection ofsimulated XRD powder patterns for zeolites”, third revised edition, M.M. J. Treacy, J. B. Higgins and R. von Ballmoos, 1996) shows that pureSAPO-20 may be formed from the above synthesis reaction by choosing anappropriate concentration region of chemical reactants.

Example 33 Preparation of SAPO-11 (ABA144-2)

The same type of AlPO powder (2.0 g) as used in Example 31(“K00-058.001”; Table 1) was mixed with Diisopropylamine (0.37 g), LudoxLS30 (0.55 g) and water (3.2 g) according to the same mixing andcrystallisation procedure as described in Example 24.

The reference XRD pattern of SAPO-11 in FIG. 12 (see “collection ofsimulated XRD powder patterns for zeolites”, third revised edition, M.M. J. Treacy, J. B. Higgins and R. von Ballmoos, 1996) confirms thatpure SAPO-11 may be formed from the above synthesis reaction by choosingan appropriate concentration region of the chemical reactants.

Examples 34-36 Varying the Time of Hydrothermal Treatment (ABA146-1, 2and 3)

Three products were prepared according to the synthesis recipe outlinedin Example 10 and using the same porous AlPO (K00-218.002, Table 1).Only the synthesis time was varied (from 20 hours to 8 hours to 4 hours,Table 2). The XRD patterns of the respective products are illustrated inFIG. 13 and show that SAPO-34 is formed after rather short time ofhydrothermal treatment, equal to or less than 4 hours. These resultsindicate that crystallisation time can be reduced substantially withoutlosing product quality, which will save production costs.

Example 37-38 Synthesis of SAPO-34 with Low Amount of StructureDirecting Agent (ABA147-2, ABA151-3)

This preparation is performed according to the mixing proceduredescribed in Examples 1-3 and using the autoclave type with Tefloninsert as described in examples 4-8. Ludox LS-30 was added to AlPO(K00-058.001) and then adding TEAOH and water under thorough mixing. Thesynthesis temperature was 210° C. for 20 h. The XRD patterns of therespective products are illustrated in FIG. 14. From these XRD patternswe see that in spite of the low amount of structure directing agentused, SAPO-34 is obtained.

Example 39 MTO Properties in a Fixed Bed Reactor

Catalytic Testing

Catalytic tests were carried out to convert methanol into light olefins.The sample of the calcined material to be tested was compressed intotablets, which were then carefully crushed. A 35-70 mesh fraction wasrecovered by sieving. 1.0 g of the powder was placed in a quartz reactorand heated to 400° C. in N₂ and kept at this temperature for 30 min,before the temperature was increased to 420° C. and a mixture of 40%methanol and 60% nitrogen was passed through it at a WHSV=1 g MeOH/gcat/h. The product stream was analysed by gas chromatography. Thecatalyst lifetime was defined as the time on stream for breakthrough ofdimethylether (t-DME defined as the time on stream when the Carbonselectivity to dimethylether (DME) in the effluent was=1%)

The product selectivity on a C-basis of the tested samples is set forthin Table 3. The results suggest that the SAPO-34 materials prepared fromsolid, porous AlPO materials by the dry syntheis method are goodcatalysts for the conversion of methanol into light olefins.

Table 3 contains catalytic results obtained on a limited selection ofthe samples shown in Table 2. The catalytic test conditions arepresented in the text. A SAPO-34 sample obtained from a “traditional”wet synthesis approach (U.S. Pat. No. 4,440,871, B. M. Lok et al., UnionCarbide 1984) was used as a reference sample. TABLE 3 The catalystlifetime given by t-DME and product selectivities at t-DME for selectedsamples. Reaction conditions 420° C., WHSV = 1 g/g, h and MeOH partialpressure 0.4 bar Product\ EWH EWH EWH EWH ABA ABA Sample 12-4 18-2 16-715-8 147-2 151-3 Reference Ethylene 44.4 42.5 42.7 39.4 42.0 43.5 45.7Propene 36.3 34.2 36.1 36.4 39.3 37.7 37.8 Butenes 11.1 11.6 11.7 13.512.0 13.2 9.9 Methane 2.0 2.0 1.8 1.8 2.6 1.5 1.2 Ethane 0.5 0.6 0.5 0.70.4 0.7 0.9 Propane 0.9 0.9 1.3 0 0 0 1.6 Butanes 0.1 0.2 0.2 0.3 0.10.3 0.1 C5+ 4.7 8.0 5.7 7.9 3.6 3.1 2.8 t-DME; 645 575 550 445 560 330400 Minutes

Example 40 MTO Properties in a Fluidized Bed Reactor

A slurry was made of the material from Example 23, the aluminiumphosphate K00-218.002 (Table 1) and SiO₂ (Ludox HS40). The slurry wasspray dried in a conventional spray drier with the outlet temperatureset at approximately 100° C. The material was then calcined in an ovenat 550° C. for 8-16 h, and the final material is denoted Prototypecatalyst. Elemental analysis of the material indicated 35 weight %SAPO-34.

The material was tested in a bench scale fluidised-bed reactor withon-line GC analysis. The results were compared with a generic SAPO-34based catalyst from UOP (id 07045-16) at identical WHSV based onSAPO-34. The catalyst lifetime defined as the time on stream forbreakthrough of dimethylether and the product selectivity are set forthin Table 4. TABLE 4 Catalyst lifetime given by t-DME and productselectivities at t-DME in the MTO reaction over the Prototype catalystand the UOP catalyst. Reaction conditions 460° C., WHSV = 1 g/g cat, hand MeOH partial pressure 0.9 bar MTO C2 = +C3 = lifetime (h)selectivity (C %) UOP catalyst 2.3 85 Prototype catalyst 2.4 86

The examples show the application of the catalyst in the synthesis oflight olefins from methanol.

Examples 41-44 Synthesis of SAPO-34/SAPO-18 with Si/Al Ratio<0.11 UsingDifferent Crystallisation Temperatures

Ludox LS30 was mixed together with TEAOH and the resulting solution wasadded to the AlPO powder (K00-218.002). The mixtures were reacted in 40ml Teflon lined stainless steel autoclaves according to the proceduredescribed in Examples 4-8. Temperatures and synthesis conditions aregiven in Table 2.

The as-synthesised catalysts were characterised by XRD to confirmformation of SAPO-34 and SAPO-18. The crystallinity as well as therelative amount of SAPO-34 and SAPO-18 was estimated by comparing theXRD diffractograms of the samples with XRD diffractograms of pureSAPO-34 and pure SAPO-18, and with theoretically calculated XRD patternsfor a product with varying composition of SAPO-34/18. The micro porevolume (MPV) was measured and the catalysts were tested for the MTOreaction according to the procedure described in Example 39.

The characterisation results are given in Table 5. The results confirmthat SAPO-34/18 materials are formed with Si/Al=0.06, and compared withSi/Al=0.17 (Example 41). SEM pictures of the samples confirm formationof small 0.1-0.6 μm particles. The examples show that by varying thesynthesis conditions the relative contents of SAPO-34 and SAPO-18 can becontrolled. The examples also show that low Si samples are very good MTOcatalysts. The low initial propane selectivity and the high catalystlifetime (t-DME) prove a low coking rate. The ethylene selectivity att-DME is high.

Examples 45-49 Synthesis of SAPO-34/18 with Si/Al=0.06, Using LowAmounts of Structure Directing Agent

Ludox LS30 was mixed together with TEAOH as well as the organicstructure directing agent TEA (Example 50) and the resulting solutionwas added to the AlPO powder (K00-218.002). The silicon content was keptat 0.06 Si/Al, but the amount of TEAOH added in the synthesis wasvaried. The mixtures were reacted in 40 ml Teflon lined stainless steelautoclaves at 210° C. for 20 h according to procedure described inExample 4-8. The synthesis conditions are given in Table 2.

The samples are characterised by XRD, MPV and tested for the MTOreaction as described in Examples 41-44. The characterisation resultsare given in Table 5 and confirm that SAPO-34/SAPO-18 samples withSi/Al=0.06 are obtained.

The examples show that by using this synthesis procedure a good MTOcatalyst can be obtained with as low as 0.33 TEAOH/Al without producingany SAPO-5 in the synthesis. Even 0.25 TEAOH/Al gives a good catalystand the small content of SAPO-5 does not interfere with the lifetime orwith the selectivity. Using 0.17 TEAOH/Al+0.17 TEA/Al also gives a goodMTO catalyst.

Example 50-51 Synthesis of SAPO-34/18 with Varying Silicon Content

Ludox LS30 was mixed together with TEAOH and the resulting solution wasadded to the AlPO powder (K00-218.002). The amount of structuredirecting agent was kept constant, but the amount of Si was varied. Themixtures were reacted in 40 ml Teflon lined stainless steel autoclavesat 210° C. for 20 h according to procedure described in Examples 4-8.The synthesis conditions are given in Table 2.

The samples are characterised by XRD, MPV and tested for the MTOreaction as described in Examples 41-44. The characterisation resultsare given in Table 5.

The examples show that by using this synthesis procedure a good MTOcatalyst is obtained with as low as 0.03 Si/Al. Example 47 shows that0.06 Si/Al gives a good MTO catalyst with the same amount of structuredirecting agent as in Examples 50 and 51. The examples (46, 49 and 51)further confirm that SAPO-34/SAPO-18 is obtained. Less TEAOH and less Sitend to increase the SAPO-18 content at these crystallisationconditions. TABLE 5 Characterisation results of catalysts in Examples41-51 Propane SAPO-34 of selectivity at SAPO-18 + TOS = 15 C₂ =selectivity Synth. Crystallinity SAPO-34³⁾ t-DME min. at t_DME MPVExample no. %²⁾ (%) (min) (%) (%) (mlN₂/g) 41 ABA-201-1 93 95 560 17 4342 ABA-201-2 62 90 560 13 43 0.20 43 ABA-202-2 86 40 670 5 44 0.23 44ABA-204-2 91 90 660 8 46 0.22 45 ABA 208-1 100   20¹⁾ 670 3 40 0.18 46ABA-207-2 92 20 625 2 40 0.20 47 ABA-208-2 80 40 48 ABA-207-1 77 50 49ABA-210-2 75   30¹⁾ 720 3 38 50 ABA-208-6 98 50 51 ABA-208-5 81 15 645 241 0.23¹⁾Small amounts of SAPO-5 is formed²⁾The crystallinity is obtained from the integral of the 2θ = 9.6,assuming SAPO-34 and SAPO-18 behaves similarly and ABA-208-1 is set to100%³⁾The relative amount of SAPO-34 and SAPO-18 was determined by comparingthe XRD diffractograms of the samples with XRD diffractograms of pureSAPO-34 and pure SAPO-18

1-22. (Cancel)
 23. Method of synthesising crystalline microporousmetalloaluminophosphate (ELAPO) from a solid body, where the bodyconsists of particles containing mainly aluminiumphosphates and wherethe pores of the particles are wholly or partly filled with a liquidreaction mixture, comprising an active source of the EL metal, anorganic structure directing agent and water, and crystallisation isperformed at elevated temperature under autogenous pressure to formcrystals of microporous ELAPO, where the EL metal is selected from thegroup consisting of silicon, magnesium, zinc, iron, cobolt, nickel,manganese, chromium and mixtures thereof.
 24. Method of synthesisingcrystalline microporous metalloaluminophosphate (ELAPO) from a solidbody, wherein the body consists of particles containing mainly EL metaland aluminiumphosphates where the pores of the particles are wholly orpartly filled with a liquid reaction mixture comprising an organicstructure directing agent and water, and crystallisation is performed atelevated temperature under autogenous pressure to form crystals ofmicroporous ELAPO where the EL metal is selected from the groupconsisting of silicon, magnesium, zinc, iron, cobolt, nickel, manganese,chromium and mixtures thereof.
 25. Method according to claim 23, whereinthe EL metal is silicon and where crystalline microporous SAPO isproduced.
 26. A method according to claim 23, wherein the AlPO₄ used hasP/Al=1.2-0.6.
 27. A method according to claim 24, wherein the liquidreaction mixture also contains an active source of a metal EL.
 28. Amethod according to claim 27, where the metal is silicon.
 29. A methodaccording to claim 23, wherein AlPO₄ particles with an outer silicashell are used.
 30. A method according to claim 23, wherein thesynthesis is carried out in the absence of an external liquid. 31.Method according to claim 23, wherein the crystallisation is performedat temperatures from 150-260° C., preferably 200-220° C.
 32. Methodaccording to claim 23, wherein the hydrothermal reaction time is 2-120hours, preferably 4-20 hours.
 33. Method according to claim 23, whereinthe particles are calcined prior to the treatment.
 34. Method accordingto claim 23, wherein the ratio between the liquid volume and pore volumeis 0.1-7, preferably 1-4 and most preferably 1-3.
 35. Method accordingto claim 23, wherein the molecular sieve is SAPO-34, SAPO-17, SAPO-18 ormixtures thereof.
 36. Method according to claim 23, wherein themolecular sieve is SAPO-5, SAPO-11 or SAPO-20.
 37. Method according toclaim 23, wherein the structure directing agent is one or more selectedfrom the group of organic structure directing agents comprisingtetraethyl ammonium hydroxide (TEAOH), isopropylamine (IPA),diisopropylamine (DPA), tripropylamine (TPA), cyclohexylamine (CHA),triethylamine (TEA) or tetramethyl-ammonium-hydroxide (TMAOH). 38.Method according to claim 23, wherein the El/Al ratio is in the range0.01-0.5, more preferably 0.03-0.17.
 39. Method according to claim 23,wherein the Si/Al ratio is in the range 0.01-0.5, more preferably0.03-0.17
 40. Method according to claim 23, wherein ELAPO is producedfrom a reaction mixture without stirring of the reactants.
 41. Amadsorbent comprising the crystalline microporous metalloaluminophosphateproduced according to claim
 23. 42. A catalyst comprising thecrystalline microporous metalloaluminophosphate produced according toclaim
 23. 43. A method for the production of olefins from an oxygenatecontaining feedstock comprising at least one compound selected from thegroup consisting of methanol, ethanol, n-propanol, iso-propanol, C4-C20alcohols, methyl ethyl ether, dimethyl ether, diethyl ether,di-isopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone,acetic acid and mixtures thereof, which comprises heating the feedstockin the presence of the crystalline microporous metalloaluminophosphateproduced according claim
 23. 44. Method according to claim 24, whereinthe EL metal is silicon and where crystalline microporous SAPO isproduced.
 45. A method according to claim 24, wherein the AlPO₄ used hasP/Al=1.2-0.6.
 46. A method according to claim 24, wherein AlPO₄particles with an outer silica shell are used.
 47. A method according toclaim 24, wherein the synthesis is carried out in the absence of anexternal liquid.
 48. Method according to claim 24, wherein thecrystallisation is performed at temperatures from 150-260° C.,preferably 200-220° C.
 49. Method according to claim 24, wherein thehydrothermal reaction time is 2-120 hours, preferably 4-20 hours. 50.Method according to claim 24, wherein the particles are calcined priorto the treatment.
 51. Method according to claim 24, wherein the ratiobetween the liquid volume and pore volume is 0.1-7, preferably 1-4 andmost preferably 1-3.
 52. Method according to claim 24, wherein themolecular sieve is SAPO-34, SAPO-17, SAPO-18 or mixtures thereof. 53.Method according to claim 25, wherein the molecular sieve is SAPO-34,SAPO-17, SAPO-18 or mixtures thereof.
 54. Method according to claim 44,wherein the molecular sieve is SAPO-34, SAPO-17, SAPO-18 or mixturesthereof.
 55. Method according to claim 24, wherein the molecular sieveis SAPO-5, SAPO-11 or SAPO-20.
 56. Method according to claim 25, whereinthe molecular sieve is SAPO-5, SAPO-11 or SAPO-20.
 57. Method accordingto claim 44, wherein the molecular sieve is SAPO-5, SAPO-11 or SAPO-20.58. Method according to claim 24, wherein the structure directing agentis one or more selected from the group of organic structure directingagents comprising tetraethyl ammonium hydroxide (TEAOH), isopropylamine(IPA), diisopropylamine (DPA), tripropylamine (TPA), cyclohexylamine(CHA), triethylamine (TEA) or tetramethyl-ammonium-hydroxide (TMAOH).59. Method according to claim 25, wherein the structure directing agentis one or more selected from the group of organic structure directingagents comprising tetraethyl ammonium hydroxide (TEAOH), isopropylamine(IPA), diisopropylamine (DPA), tripropylamine (TPA), cyclohexylamine(CHA), triethylamine (TEA) or tetramethyl-ammonium-hydroxide (TMAOH).60. Method according to claim 44, wherein the structure directing agentis one or more selected from the group of organic structure directingagents comprising tetraethyl ammonium hydroxide (TEAOH), isopropylamine(IPA), diisopropylamine (DPA), tripropylamine (TPA), cyclohexylamine(CHA), triethylamine (TEA) or tetramethyl-ammonium-hydroxide (TMAOH).61. Method according to claim 24, wherein ELAPO is produced from areaction mixture without stirring of the reactants.
 62. An adsorbentcomprising the crystalline microporous metalloaluminophosphate producedaccording to claim
 24. 63. A catalyst comprising the crystallinemicroporous metalloaluminophosphate produced according to claim
 24. 64.A method for the production of olefins from an oxygenate containingfeedstock comprising at least one compound selected from the groupconsisting of methanol, ethanol, n-propanol, iso-propanol, C4-C20alcohols, methyl ethyl ether, dimethyl ether, diethyl ether,di-isopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone,acetic acid and mixtures thereof, which comprises heating the feedstockin the presence of the crystalline microporous metalloaluminophosphateproduced according claim 24.